Water-insoluble metal salts of phthalocyanine-sulphonic acids



Patented Nov. 23, 1937 UNITED STATES 2,099,039 Y wsraa-msowam METAL SALTS or PHTHALOOYANINE-SULPHONIC ACIDS Holracirh and Georgd Niemann, Ludwigen-one-Bliine, ermany asslgnora to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application April 18, 1938, Serial No. 75,234. In Germany April 20, 1935 7 Claims. (01. zoo-11 The present invention relates to water-insoluble metal salts of phthalocyanine sulphonic acids.

By heating derivatives of aromatic ortho-dicarboxylic acids which are iormed by the combination of nitrogen to the carbon atoms oi the two adjacent carboxylic groups,,or their substitution products, such as phthalodinitrile, ortho-cyanopenzamide or naphthalene ortho-dicarboxylic acid dinitrils, either alone or together with metals or metal compounds or other substances, valuable colored products. the so-called phthalocyanines, are obtained which may be subsequently sulphonated when they do not already contain sulphonlc groups.

Wehavenowioundthatvaluablewater-insoluble salts of the sulphonic acids of the phthalocyanines which hereinafter are called color lakes, can be obtained by treating, in aqueous solution, the said sulphonic acids with metal compounds suitable for laking, in particular soluble metal salts, metal oxides or metal hydroxides. The sulphonic acids, in the form of their alkali metal salts, are soluble in water giving a deep blue coloration and are preferably employed as such according to this invention. Suitable metal compounds for laking are for example the soluble salts, oxides and hydroxides of calcium, strontium, barium, magnesium, aluminium, iron, cobalt, zinc, manganese and nickel. In many cases it is advantageous to allow the laking to take place in the presence of additional substances such as resin soaps, soluble synthetic resins or dispersing agents. Either a neutral, acid or alkaline medium may be employed.

The following examples will further illustrate how the said invention may be carried out in practice but the invention is not restricted to these examples. The parts are by weight.

Example 1 7 parts of the sodium salt of the sulphonic acid of the blue substance obtainable by heating phthalodinitrile in the presence of cuprous chloride and pyridine (prepared by sulphonation of the blue substance with five times the amount of 30 per cent oleum while heating for an hour at 0., pouring onto ice and neutralizing by the addition of sodium carbonate with subsequent salting out) are dissolved in parts 01 water, heated and precipitated by the addition of 9 parts of barium chloride. A brilliant green-blue color lake is obtained.

A corresponding amount of calcium chloride or zinc chloride may be employed'instead of barium chloride. A similar procedure is followed when employing magnesium or manganese salts tor the laking.

' Example 2 20 parts of heavy spar are suspended in a solution or 10 parts of aluminium sulphate and 5 parts of soda in parts of water and mixed with a solution of 12 parts of barium chloride in 88 parts of water. The precipitate is washed by repeatedly spraying it with water and decanting and suspended in a solution of 1.5 parts of the sulphonic acid of copper phthalocyanine (of. Example l) and 1.5 parts oi the azo dyestufi from diazotized 1,2,5-aniline-sulphonic acid and 1 (2 ',5 -disulphophenyl) 5 pyrazolone- 3-carboxylic acid in 300 parts of water. The dyestufl is precipitated by adding a solution of 3 parts of barium chloride in 30 parts of water. The color paste separated by filtration may be brushed onwall paper together with vegetable glue, a fast, brilliant green painting being obtained.

More greenish color shades are obtained if instead oi a copper-phthalocyanine-sulphonic acid, a sulphonic acid of the phthalocyanine tree from metal is employed.

Example 4 2 parts of the sodium salt of the nickel-phthalocyanine-sulphonic acid prepared by causing 300 parts of 33 per cent oleum to act on 30 parts of a nickel-phthalocyanine (obtainable by heating ortho-phthalodinitrile and nickelous chloride in the presence of quinoline at between 200 and 210 C. for several hours) at 25 0. within 2 hours, are dissolved in 1000 parts of water. To this solution there is added a precipitate freshly prepared from 20 parts of barium sulphate, 10 parts of a .10 per cent aqueous solution of aluminium sulphate, 5 parts of an about 10 per cent aqueous solution of sodium carbonate and 12 parts of an about 10 per cent aqueous solution of barium chloride.

The color lake is then precipitated on the substratum by theaddition oi 3 parts of barium chloride. The color paste obtained yields a brilliant green-blue coating. 7

. laampls 5 A xinc-phthalocyanine-sulphonic acid obtained by treating 80 parts at linc-phthalocyae nine prepared ior example by heating orthophthalodinitrile with zinc oxide and iormamide with 300 parts oi 33 per cent oleum at 50, 0. within 85 minutes is made into b labs in the manner described in Example 4. A brilliant green. color lake is thus obtained 5 x mpl 6 100 parts oi copper phthalocya'nine are entered into a mixture of 500 parts oi sulphuric acid monohydrate and 500 parts oi 65 per cent oleum and kept at 25 C. for 24 hours. The mixture is then poured onto ice and the resulting copperphthalocyaninemonosulphonic acid is converted into the sodium salt in known manner. The dyestuii thus obtained is introduced into M900 parts oi water, mixed with 100 parts oi a 10 per cent solution of resin soap and precipitated by means oi 280 parts oi a 10 percent solution oi barium chloride. The color lake is allowed to deposit, decanted and then pressed oii. It has a brilliant blue shade.

E's-ample 7 2,3-dicyan-naphthalene is converted into a phthalocyanine by' heating it with a mixture 01 nitroben'zena'pyridine and cuprous chloride. The resulting dyestuii is sulphonated by treating it with 30 per cent oleum at room temperature.

The scdiumsalt oi this sulphonic acid which is readily soluble in water is made into a lake in the manner similar to that of Example 4. A brilliant green color lake is thus obtained which is especially suitable for coloring wall papers.

Example 8 per-phthalocyanine.

' per-phthalocyanine.

I'm 9 80 parts oi heavy spar are made into apaste with 10 parts oi a ioperoent aqmoussolutionoi aluminium sulphate which latter is transiormed' into aluminium hydroxide by the addition oi 5 partsloi a 10 per cent aqueous solution oi anhydrous sodium carbonate. whereupon 12 parts gia 10 per cent aqueous solution oi barium chloride are added to this mixture oi heavy spar and aluminium hydroxide ior the iormation oi blanciix. 8 parts oi a 1 per cent aqueous solution oi the sodium salt oi the sulphonic acid oi copper phthalocyanine are added to the said substratum oi heavy spar. aluminium hydroxide'and blancflx, the said substratum having been careiully washed, and the pigment is precipitated, by

means oi 4 parts oi a 10 per cent aqueous solution oi barium chloride. A color lake havina a brilliant Bremen blue color shade is thus obtained. Instead oi barium chloride there may also be employed a corresponding amount oi calcium chloride or zinc chloride as well as oi salts oi other metals. such as aluminium sulphate.

Instead of the said substratum other substrata usual in the'color lake industry may also be used, such as lithopone, zinc white or calc spar.

What we claim is:- I l. A water-insoluble metal salt oi a phthalocyanine sulphonic acid.

2. A water-insoluble metal salt oi a sulphonic acid oi a metal-containing phthalocyanine.

a. A water-insoluble salt oi a light metal se- 1 lected irom the second and third groups oi the periodic system of a sulphonic acid oi a metalcontaining phthalocyanine.

4.1L water-insoluble salt oi a light metal selected irom the second and third groups ,oi the periodic system oi a sulphonic acid oi copperphthalocyanine.

5. The aluminium salt oi a sulphonic acid oi copper-phthalocyanine.

6. The barium salt oi a sulphonic acid oi cope 7. The calcium salt oi a sulphonic acid oi copmm. rrprzsc n. .j (mono museum. 

